Certain substituted bis(2-benzoyl-3-oxo-cyclohexenyl) thioglycols

ABSTRACT

An herbicide compound of the formula ##STR1## wherein R is halogen, C 1  -C 2  alkyl, C 1  -C 2  alkoxy, nitro; cyano; C 1  -C 2  haloalkyl, or R a  SO n  -- wherein n is 0 or 2 and R a  is C 1  -C 2  alkyl; 
     R 1  is hydrogen or C 1  -C 4  alkyl; 
     R 2  is hydrogen or C 1  -C 4  alkyl; or 
     R 1  and R 2  together are alkylene having 2 to 5 carbon atoms; 
     R 3  is hydrogen or C 1  -C 4  alkyl; 
     R 4  is hydrogen or C 1  -C 4  alkyl; or 
     R 3  and R 4  together are oxo; 
     R 5  is hydrogen or C 1  -C 4  alkyl; 
     R 6  is hydrogen or C 1  -C 4  alkyl; or 
     R 5  and R 6  together are alkylene having 2 to 5 carbon atoms; 
     R 7  and R 8  independently are (1) hydrogen; (2) halogen; (3) C 1  -C 4  alkyl; (4) C 1  -C 4  alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1  -C 4  haloalkyl; (9) R b  SO n  --wherein n is the integer 0, 1 or 2; and R b  is (a) C 1  -C 4  alkyl; (b) C 1  -C 4  alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR c  R d  wherein R c  and R d  independently are hydrogen or C 1  -C 4  alkyl; (11) R e  C(O)-- wherein R e  is C 1  -C 4  alkyl or C 1  -C 4  alkoxy; (12) SO 2  NR c  R d  wherein R c  and R d  are as defined; (13) --N(R c )C(O)R d  wherein R c  and R d  are as defined; or (14) --CH 2  CH 2  OCH 3  or --CH 2  CH 2  OC 2  H 5  ; with the proviso that R 7  is not at the 6-position; and 
     R 9  is C 2  -C 6  alkylene.

BACKGROUND OF THE INVENTION

Herbicidal compounds having the structural formula ##STR2## wherein R through R⁸ are as defined below and m is the integer 0,1 or 2, and R⁹ is C₁ -C₄ alkyl, phenyl, substituted phenyl, cyano; --(CH₂)_(x) C(O)O--(C₁ -C₄ alkyl); wherein x is the integer 1, 2 or 3; are described in U.S. Pat. No. 4,837,352 which is incorporated herein by reference.

DESCRIPTION OF THE INVENTION

This invention relates to certain substituted bis(2-benzoyl-3-oxo-cyclohexenyl)thioglycols and their use as herbicides.

One embodiment of this invention is an herbicidal composition comprising an herbicidally active substituted bis(2-benzoyl-3-oxo-cyclohexenyl)thioglycols and an inert carrier therefor wherein the 2-position of each benzoyl moiety is substituted as herein recited and the 4-position preferably is substituted with an electron withdrawing group such as halogen, cyano, trifluoromethyl or nitro. The 4-, 5- and 6-positions of each cyclohex-2-enone moiety can be substituted, preferably with the groups hereinafter recited. More preferably, the cyclohex-2-enone moieties have no substitution or the 4- or 6-positions are substituted with one or two methyl groups. The 3-, 4- and 5-positions of the benzoyl moieties can be substituted, preferably with the groups hereinafter recited.

Also embodied within the scope of this invention are novel compounds having the following structural formula ##STR3##

R is halogen; C₁ -C₂ alkyl, preferably methyl; C₁ -C₂ alkoxy, preferably methoxy; nitro; cyano; C₁ -C₂ haloalkyl, preferably trifluoromethyl; or R^(a) SO_(n) -- wherein n is 0 or 2, preferably 2 and R^(a) is C₁ -C₂ alkyl, preferably methyl. Preferably, R is chlorine, bromine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, cyano, nitro, C₁ -C₂ alkylthio or C₁ -C₂ alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl;

R¹ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl, most preferably R¹ is hydrogen or methyl;

R² is hydrogen; C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl, most preferably R² is hydrogen or methyl; or

R¹ and R² together are alkylene having 2 to 5 carbon atoms;

R³ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl, most preferably R³ is hydrogen or methyl;

R⁴ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl, most preferably R⁴ is hydrogen or methyl; or

R³ and R⁴ together are oxo;

R⁵ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl, most preferably R⁵ is hydrogen or methyl;

R⁶ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl, most preferably R⁶ is hydrogen; or

R⁵ and R⁶ together are alkylene having 2 to 5 carbon atoms;

R⁷ and R⁸ independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ alkoxy, preferably methoxy or ethoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 0 or 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen, preferably chloromethyl, or trifluoromethyl or cyano;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; (13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined; and (14) --CH₂ CH₂ OCH₃ or --CH₂ CH₂ OC₂ H₅ ; with the provision that R⁷ is not in the 6-position; and

R⁹ is C₂ -C₆ alkylene, preferably C₂ -C₄ alkylene, more preferably ethylene.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The term "C₁ -C₄ alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "C₁ -C₄ haloalkyl" includes the alkyl groups defined above under C₁ -C₄ alkyl in which one or more hydrogen is replaced by chloro, bromo, iodo or fluoro.

Preferably, R is chlorine, bromine, nitro, methyl or trifluoromethyl, preferably R⁷ is in the 3-position. More preferably R⁷ is hydrogen, C₁ -C₄ alkoxy, --CH₂ CH₂ OCH₃, --CH₂ CH₂ OC₂ H₅, or C₁ -C₄ thioalkyl. More preferably, R⁷ is hydrogen, methylthio, methoxy, ethoxy, --CH₂ CH₂ OCH₃ or --CH₂ CH₂ OC₂ H₅. Most preferably, R⁸ is halogen, trifluoromethyl, or R^(b) SO_(n) wherein R^(b) is C₁ -C₄ alkyl, preferably methyl or ethyl, and n is the integer 0 or 2.

The compounds of this invention are active herbicides of a general type. That is, they are herbicidally effective against a wide range of plant species. The method of controlling undesirable vegetation of the present invention comprises applying an herbicidally effective amount of the above-described compounds to the area where control is desired.

The compounds of the present invention can be prepared by the following two-step general method. ##STR4## wherein R through R⁸ are as defined.

Generally, in step (a) the benzoyl dione is dissolved in an inert solvent such as methylene dichloride and an excess, usually 150 to 200 mole percent, of oxalyl chloride is added followed by a catalytic amount (0.1 equivalent) of dimethylformamide. The reaction mixture is stirred from one hour to one day at room temperature. The reaction product is isolated using conventional techniques. ##STR5## wherein R through R⁹ are as defined.

Generally, in step (b) 2 mole of the 3-chloro-2-benzoylcycloalk-2-enone are reacted with a mole of the thioglycol and a mole of a non-nucleophilic base such as triethylamine in an inert solvent. The mixture is stirred 1 to 18 hours and the desired product is isolated using conventional techniques.

The following examples teach the synthesis of a representative compound of this invention.

EXAMPLE I 3-Chloro 6,6-dimethyl-2-(2-nitro-4-methanesulfonylbenzoyl) cyclohex-2-enone ##STR6## 2-(2-nitro-4-methanesulfonylbenzoyl)-cyclohexane-1,3-dione (11.4 grams (g), 30 millimole (mmol)) was dissolved in 100 milliliters (mL) methylene chloride and stirred at room temperature. To this solution was added oxalyl chloride (5.7 g, 45 mmol) followed by dimethylformamide (0.5 mL) in portions small enough to control effervescence. The resulting solution was stirred for 4 hours and then poured into water and extracted with methylene chloride. The organic layer was washed again with water, saturated K₂ CO₃ solution and then dried with MgSO₄ and the solvent evaporated to yield 3-chloro-2-(2-nitro-4-methanesulfonylbenzoyl)-6,6 dimethyl cyclohex-2-enone (7.3 g, 61 percent (%)) as an oil which was used without further purification. EXAMPLE II S,S'-di(2-(2-nitro-4-methanesulfonylbenzoyl)-3-oxo-4,4-dimethyl-cyclohexenyl)thioethylene glycol ##STR7## 3-Chloro-6,6-dimethyl-2(2-nitro-4-methanesulfonylbenzoyl) cyclohex-2-enone (5.7 g, 14.8 mmol) was dissolved in 100 mL methylene chloride and stirred at room temperature. To this solution was added a mixture of 1,2-ethanedithiol 6.70 g, 7.4 mmol) and triethylamine (1.5 g, 14.8 mmol), and the solution stirred for 2 hours at room temperature and then heated under reflux for 2 hours. After cooling the mixture, additional methylene chloride was added and the organic layer was washed with 2N HCl, saturated NaCl solution, saturated NaHCO₃ solution, dried with MgSO₄ and the solvent evaporated almost to dryness. The resulting oil was then titurated with ether to obtain 4.3 g of a brown solid. To further purify and separate the resulting mixture, column chromatography was done using silica and 1:1 hexane:ethyl acetate as eluent yielding 2.6 g of a solid Spectroscopic data: 'H nuclear magnetic resonance (NMR), ¹³ C NMR, infra red, and mass spectroscopy are consistent with the proposed structure.

The following is a table of certain selected compounds that are preparable according to the procedure described herein. Compound numbers are assigned to each compound and are used throughout the remainder of the application.

                                      TABLE I                                      __________________________________________________________________________      ##STR8##                                                                      Cmpd.                                                                          No. R  R.sup.1                                                                           R.sup.2                                                                           R.sup.3                                                                           R.sup.4                                                                          R.sup.5                                                                           R.sup.6                                                                           R.sup.7                                                                               R.sup.8 R.sup.9                                 __________________________________________________________________________     1..sup.a)                                                                          NO.sub.2                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H  H H  H  H      SO.sub.2 CH.sub. 3                                                                     CH.sub.2 CH.sub.2                       2.  Cl H  H  CH.sub.3                                                                          H H  H  3-OCH.sub.2 CH.sub.3                                                                  SO.sub.2 CH.sub.2 CH.sub.3                                                             CH.sub.2 CH.sub.2                       3.  Cl H  H  H  H H  H  3-OCH.sub.2 CN.sub.3                                                                  SO.sub.2 CH.sub.3                                                                      CH.sub.2 CH.sub.2                       4.  NO.sub.2                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H  H H  H  H      H       CH.sub.2 CH.sub.2                       5.  NO.sub.2                                                                          CH.sub.3                                                                          CH.sub.3                                                                          O    CH.sub.3                                                                          CH.sub.3                                                                          H      CF.sub.3                                                                               CH.sub.2 CH.sub.2                       6.  Cl H  H  H  H H  H  3-Cl   Cl      CH.sub.2 CH.sub.2                       __________________________________________________________________________      .sup.a) Prepared in Example I.                                           

Herbicidal Screening Tests

As previously mentioned, the herein described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in controlling various plant species. Selected compounds of this invention were tested as herbicides in the following manner.

Pre-emergence Multi-weed Herbicide Test: On the day preceding treatment, seeds of several different weed species are planted in loamy sand soil in individual rows using one species per row across the width of a flat. The weeds used are blackgrass (ALOMY) (Alopecurus myosuroides), wild oat, (AVEFA) (Avena fatua), broadleaf signalgrass (BRAPP) (Brachiaria platphylla), watergrass (ECHCG) (Echinochloa crusgalli), giant foxtail (SETFA) (Setaria faberi), green foxtail (SETVI) (Setaria viridis), velvetleaf (ABUTH) (Abutilon theophrasti), redroot pigweed (AMARE) (Amaranthus retroflexus), sicklepod (CASOB) (Cassia obtusifolia), morningglory (IPOSS) (Ipomoea sp.), scented mayweed (MATCH) (Matricaria recutita), annual morningglory (PHBPU) (Ipomoea purpurea), hemp sesbania (SEBEX) (Sesbania exaltata), wild mustard (SINAR) (Brassica kaber), common chickweed (STEME) (Stellaria media), cocklebur (XANPE) (Xanthium pensylvanicum), and yellow nutsedge (CYPES) (Cyperus esculentus). Ample seeds are planted to give about 20 to 40 seedlings per row, after emergence, depending upon the size of the plants.

Using an analytical balance, 400 milligrams (mg) of the compound to be tested are weighed out on a piece of glassine weighing paper. The paper and compound are placed in a 60 milliliter (ml) wide-mouth clear bottle and dissolved in a solution of 20 ml of acetone and 20 ml water containing enough polyoxyethylene sorbitan monolaurate emulsifier to give a final solution of 0.5% (v/v). The solution is then sprayed on a seeded flat on a linear spray table calibrated to deliver 400 L/ha. The application rate was 4.0 kg/ha.

After treatment, the flats are placed in the greenhouse at a temperature of 70° to 80° F and watered by sprinkling. Two weeks after treatment, the degree of injury or control is determined by comparison with untreated check plants of the same age. The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no injury and 100% representing complete control.

Several compounds were evaluated at an application rate of 1.0 or 0.25 kg/ha for pre- and post-emergence activity against several of the weed species that are listed in the above-described pre-emergent multi-herbicide test.

The process was generally similar to the pre-emergence herbicide test procedure described above except that only 1000 or 250 milligrams of test compound were weighted out.

The results of the 4.0 kg/ha pre-emergence test are shown in Table II. The results of the 1.0 kg/ha pre- and post-emergence test are shown in the following Table IV. The results of the 0.25 kg/ha pre-emergence test are shown in the Table VI.

                                      TABLE II                                     __________________________________________________________________________     Pre-emergence Herbicidal Activity                                              Application Rate - 4.0 kg/ha                                                   Compd.                                                                         No.  AVEFA                                                                               ECHCG                                                                               SETVI                                                                              ABUTH                                                                               PHBPU                                                                               SINAR                                                                               CYPES                                        __________________________________________________________________________     1    80   100  100 100  100  100  95                                           4    40   90    50 100  10   100  80                                           5    75   20   100 100  10    95   0                                           __________________________________________________________________________      (--) = Not tested.                                                       

Post-emergence Multi-weed Herbicide Test: This test is conducted in an identical manner to the testing procedure for the pre-emergence multi-weed herbicide test, except the seeds of the eight different weed species are planted 10-12 days before treatment. Also, watering of the treated flats is confined to the coil surface and not to the foliage of the sprouted plants.

The results of the post-emergence multi-weed herbicide test are reported in Tables III, V and VII.

                                      TABLE III                                    __________________________________________________________________________     Post-emergence Multi-weed Herbicidal Activity                                  Application Rate - 4.0 kg/ha                                                   Compd.                                                                         No.  AVEFA                                                                               ECHCG                                                                               SETVI                                                                              ABUTH                                                                               PHBPU                                                                               SINAR                                                                               CYPES                                        __________________________________________________________________________     1    85   100  100 100  100  100  95                                           4    80   90   100 100  80   100  80                                           5    10   10    10 100  20    40  10                                           __________________________________________________________________________      (--) = Not tested.                                                       

                                      TABLE IV                                     __________________________________________________________________________     Pre-emergence Herbicidal Activity                                              Application Rate - 1.0 kg/ha                                                   __________________________________________________________________________     Compd.                                                                         No.  ALOMY                                                                               AVEFA                                                                               BRAPP                                                                               ECHCG                                                                               SETFA                                                                               ABUTH                                                                               AMARE                                                                               CASOB                                                                               IPOSS                             __________________________________________________________________________     3    10   20   100  100  60   100  10   35   65                                __________________________________________________________________________                             Compd.                                                                         No.  MATCH                                                                               SEBEX                                                                               STEME                                                                               XANPE                              __________________________________________________________________________                             3    100  100  100  --                                 __________________________________________________________________________      (--) = Not tested.                                                       

                                      TABLE V                                      __________________________________________________________________________     Post-emergence Herbicidal Activity                                             Application Rate - 1.0 kg/ha                                                   __________________________________________________________________________     Compd.                                                                         No.  ALOMY                                                                               AVEFA                                                                               BRAPP                                                                               ECHCG                                                                               SETFA                                                                               ABUTH                                                                               AMARE                                                                               CASOB                                                                               IPOSS                             __________________________________________________________________________     3    5    20   85   100  65   100  15   5    85                                __________________________________________________________________________                             Compd.                                                                         No.  MATCH                                                                               SEBEX                                                                               STEME                                                                               XANPE                              __________________________________________________________________________                             3    100  90   100  75                                 __________________________________________________________________________      (--) = Not tested.                                                       

                                      TABLE VI                                     __________________________________________________________________________     Pre-emergence Herbicidal Activity                                              Application Rate - 0.25 kg/ha                                                  Compd.                                                                         No.  ECHCG                                                                               SETFA                                                                               SORVU                                                                               ABUTH                                                                               CASOB                                                                               IPOSS                                                                              AMARE                                                                               XANST                                                                               CYPES                              __________________________________________________________________________     2    0    0    0    20   0    10  50   0    0                                  __________________________________________________________________________      (--) = Not tested.                                                       

                                      TABLE VII                                    __________________________________________________________________________     Post-emergence Herbicidal Activity                                             Application Rate - 0.25 kg/ha                                                  Compd.                                                                         No.  ECHCG                                                                               SETFA                                                                               SORVU                                                                               ABUTH                                                                               CASOB                                                                               IPOSS                                                                              AMARE                                                                               XANST                                                                               CYPES                              __________________________________________________________________________     2    0    0    0    40   0    0   0    --   0                                  __________________________________________________________________________      (--) = Not tested.                                                       

The compounds of the present invention are useful as herbicides and can be applied in a variety of ways at various concentrations. In practice, the compounds herein defined are formulated into herbicidal compositions, by admixture, in herbicidally effective amounts, with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the materials in a given application. Thus, these active herbicidal compounds may be formulated as granules of relatively large particle size, as wettable powders, as emulsifiable concentrates, as powdery dusts, as solutions or as any of several other known types of formulations, depending upon the desired mode of application. Preferred formulations for pre-emergence herbicidal applications are wettable powders, emulsifiable concentrates and granules. These formulations may contain as little as about 0.5% to as much as about 95% or more by weight of active ingredient. A herbicidally effective amount depends upon the nature of the seeds or plants to be controlled and the rate of application varies from about 0.05 to approximately 10 pounds per acre, preferably from about 0.1 to about 4 pounds per acre.

Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants. The wettable powder is ultimately applied to the soil either as a dry dust or as a dispersion in water or other liquid. Typical carriers for wettable powders include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic diluents. Wettable powders normally are prepared to contain about 5% to about 95% of the active ingredient and usually also contain a small amount of wetting, dispersing, or emulsifying agent to facilitate wetting and dispersion.

Emulsifiable concentrates are homogeneous liquid compositions which are dispersible in water or other dispersant, and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthal, isophorone and other non-volatile organic solvents. For herbicidal application, these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises about 0.5% to 95% of active ingredient by weight of the herbicidal composition.

Granular formulations wherein the toxicant is carried on relatively coarse particles, are usually applied without dilution to the area in which suppression of vegetation is desired. Typical carriers for granular formulations include sand, fuller's earth, bentonite clays, vermiculite, perlite and other organic or inorganic materials which absorb or which may be coated with the toxicant. Granular formulations normally are prepared to contain about 5% to about 25% of active ingredients which may include surface-active agents such heavy aromatic naphthas, kerosene or other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.

Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; polyhydric alcohols; and other types of surface-active agents, many of which are available in commerce. The surface-active agent, when used, normally comprises from 0.1% to 15% by weight of the herbicidal compositions.

Dusts, which are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers for the toxicant, are useful formulations for soil-incorporating application.

Pastes, which are homogeneous suspensions of a finely divided solid toxicant in a liquid carrier such as water or oil, are employed for specific purposes. These formulations normally contain about 5% to about 95% of active ingredient by weight, and may also contain small amounts of a wetting, dispersing or emulsifying agent to facilitate dispersion. For application, the pastes are normally diluted and applied as a spray to the area to be affected.

Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprays, typically aerosols, wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used.

The phytotoxic compositions of this invention are applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions are applied to the soil according to conventional methods and are distributed in the soil to a depth of at least 1/2 inch below the soil surface. It is not necessary that the phytotoxic compositions be admixed with the soil particles since these compositions can also be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations.

    __________________________________________________________________________     General Formula with Ranges                                                                       Specific Formula                                            __________________________________________________________________________     EMULSIFIABLE CONCENTRATE FORMULATIONS                                          herbicidal compound                                                                        5-55   herbicidal compound                                                                        54                                              surfactant(s)                                                                              5-25   proprietary blend of oil-                                                                  10                                              solvent(s) 20-90   soluble sulfonates and                                                 100%    polyoxyethylene ethers                                                         polar solvent                                                                              27                                                                 petroleum hydrocarbon                                                                       9                                                                              100%                                           WETTABLE POWDER FORMULATIONS                                                   herbicidal compound                                                                        3-90   herbicidal compound                                                                        80                                              wetting agent                                                                             0.5-2   sodium dialkyl                                                                               0.5                                           dispersing agent                                                                          1-8     naphthalene sulfonate                                       diluent(s) 8.5-87  sodium lignosulfonate                                                                       7                                                         100%    attapulgite clay                                                                             12.5                                                                          100%                                           EXTRUDED GRANULAR FORMULATIONS                                                 herbicidal compound                                                                        1-20   herbicidal compound                                                                        10                                              binding agent                                                                              0-10   lignin sulfonate                                                                            5                                              diluent(s) 70-99   calcium carbonate                                                                          85                                                         100%                 100%                                           FLOWABLE FORMULATIONS                                                          herbicidal compound                                                                       20-70   herbicidal compound                                                                        45                                              surfactant(s)                                                                              1-10   polyoxyethylene ether                                                                       5                                              suspending agent(s)                                                                       0.05-1  attagel        0.05                                         antifreeze agent                                                                           1- 10  propylene glycol                                                                           10                                              antimicrobial agent                                                                        1-10   BIT            0.03                                         antifoam agent                                                                            0.1-1   silicone defoamer                                                                             0.02                                         solvent     7.95-76.85                                                                            water         39.9                                                     100%                 100%                                           __________________________________________________________________________

The phytotoxic compositions of this invention can also contain other additives, for example, fertilizers, other herbicides and other pesticides, used as adjuvant or in combination with any of the above-described adjuvants. Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate.

The herbicidal compounds of this invention can be used in combination with other herbicidal compounds for broader spectrum control of undesirable vegetation. Examples of other herbicidal compounds are as follows:

1. Anilides

Alachlor--2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide

Metolachlor--2-chloro-2'-methyl-6'ethyl-N-methoxy-isopropyl-2-acetanilide

Propanil--N-(3,4-dichlorophenyl)propionanilide

Acetachlor--2-chloro-2'-methyl-6'ethyl-N-ethoxymethylacetanilide

2. Triazines

Atrazine--2-chloro-4-(ethylamino)-6-isopropylamino)-s-triazine

Cyanazine--2-chloro-4-(1-cyano-1-methylethylamino)-6-ethylamino-s-triazine

Metribuzin--4-amino-6 -tert-butyl-3-(methylthio)-1,2,4-triazin-5(4H)-one

3. Thiocarbamates

Molinate--S-ethyl hexahydro-1H-azepine-1-carbothioate

Butylate--S-ethyl diisobutylthiocarbamate

4. Ureas

Monuron--3-(p-chlorophenyl)-1,1-dimethylurea

Linuron--3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea

5. Toluidines

Trifluralin--α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine

Pendimethalin--N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzeneamine

6. Hormones

2,4-D--(2,4-dichlorophnoexy) acetic acid

MCPA--(2-methyl-4-chlorophenoxy) acetic acid

7. Diazines

Bentazon--3-isopropyl-1H-2,3,1-benzothiadiazin-4(3H)-one 2,2-dioxide

Oxadiazon--2-tert-butyl-4-(2,4-dichloro-5-isopropoxyphenyl)-Δ² -1,3,4-oxadiazolin-5-one

8. Diphenyl ethers

Acifluorfen--sodium 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate

Fluazifop-butyl -(±)-butyl 2-[4[(5-(trifluoromethyl)-2-pyridinyl)oxy]phenoxy]propanoate

Chlomethoxynil--2,4-dichlorophenyl 3-methoxy-4-nitrophenyl ether

9. Imidazolinones

Imazaquin--2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3-quinolin carboxylic acid

10. Sulfonyl ureas

Bensulfuron methyl--methyl 2-[[[[[(4,6-dimethoxypyridimidin-2-yl)amino]carbonyl]amino]sulfonyl]methyl]benzoate

Chlorimuron ethyl--ethyl 2-(((((4-chloro-6-methoxypyrimidin-2-yl)amino)carbonyl)amino)sulfonyl) benzoate

11. 2-(2-Substituted benzoyl)-1,3-cyclohexanediones

2- (2'-chloro-4-methysulfonyl benzoyl)-1,3-cyclohexanedione

12. Miscellaneous compounds

Dimethazone--2-(2-chlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone

Norflurazon--4-chloro-5-(methylamino)-2-α,α,α-trifluoro-m-tolyl)-3-(2H)-pyridazinone

Dalapon--2,2-dichloropropionic acid

Glyphosate--isopropyl amine salt of N-(phosphonomethyl) glycine

Fenoxaprop-ethyl--(+)-ethyl-2,4-((6-chloro-2-benzoxazolyloxy)phenoxy)propanoate 

What is claimed is:
 1. A compound of the formula ##STR9## wherein R is halogen, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, nitro; cyano; C₁ -C₂ haloalkyl, or R^(a) SO_(n) -- wherein n is 0 or 2 and R^(a) is C₁ -C₂ alkyl;R¹ is hydrogen or C₁ -C₄ alkyl; R² is hydrogen or C₁ -C₄ alkyl; or R¹ and R² together are alkylene having 2 to 5 carbon atoms; R³ is hydrogen or C₁ -C₄ alkyl; R⁴ is hydrogen or C₁ -C₄ alkyl; or R³ and R⁴ together are oxo; R⁵ is hydrogen or C₁ -C₄ alkyl; R⁶ is hydrogen or C₁ -C₄ alkyl; or R⁵ and R⁶ together are alkylene having 2 to 5 carbon atoms; R⁷ and R⁸ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; (12) SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; (13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined; or (14) --CH₂ CH₂ OCH₃ or --CH₂ CH₂ OC₂ H₅ ; with the proviso that R⁷ is not at the 6-position; and R⁹ is C₂ -C₆ alkylene.
 2. The compounds of claim 1 wherein R is chlorine, bromine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, nitro, C₁ -C₂ alkylthio or C₁ -C₂ alkylsulfonyl; R¹ is hydrogen or methyl; R² is hydrogen or methyl; R³ is hydrogen or methyl; R⁴ is hydrogen or methyl; R⁵ is hydrogen or methyl; R⁶ is hydrogen or methyl; R⁷ and R⁸ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n is the integer 0 or 2; and R^(b) is (a) C₁ -C₂ alkyl; or (b) C₁ -C₂ alkyl substituted with halogen or (10) --CH₂ CH₂ OCH₃ or --CH₂ CH₂ OC₂ H₅ ; and R⁹ is is C₂ -C₄ alkylene.
 3. The compound of claim 2 wherein R⁷ is hydrogen, methylthio, methoxy, ethoxy, --CH₂ CH₂ OCH₃ or --CH₂ CH₂ OC₂ H₅ and is in the 3-position, and R⁸ is hydrogen, chlorine, bromine, fluorine, trifluoromethyl or R^(b) SO_(n) wherein R^(b) is C₁ -C₃ alkyl and n is the integer 0 or
 2. 4. The compound of claim 2 wherein R is chlorine; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is 3-ethoxy; R⁸ is 4-methylsulfonyl; and R⁹ is ethylene.
 5. The compound of claim 2 wherein R is nitro; R¹ is methyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is hydrogen; and R⁹ is ethylene.
 6. The compound of claim 2 wherein R is chlorine; R¹ is hydrogen; R² is hydrogen; R³ is methyl; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is 3-ethoxy; R⁸ is 4-CH₃ SO₂ --; and R⁹ is ethylene.
 7. The compound of claim 2 wherein R is nitro; R¹ is methyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is hydrogen; and R⁹ is ethylene.
 8. The compound of claim 2 wherein R is chloro; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is 3-chloro; R⁸ is 4-chloro; and R⁹ is ethylene.
 9. The method of controlling undesirable vegetation comprising applying to the area where control is desired, an herbicidally effective amount of a compound having the formula ##STR10## wherein R is halogen, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, nitro; cyano; C₁ -C₂ haloalkyl, or R^(a) SO_(n) -- wherein n is 0 or 2 and R^(a) is C₁ -C₂ alkyl;R¹ is hydrogen or C₁ -C₄ alkyl; R² is hydrogen or C₁ -C₄ alkyl; or R¹ and R² together are alkylene having 2 to 5 carbon atoms; R³ is hydrogen or C₁ -C₄ alkyl; R⁴ is hydrogen or C₁ -C₄ alkyl; or R³ and R⁴ together are oxo; R⁵ is hydrogen or C₁ -C₄ alkyl; R⁶ is hydrogen or C₁ -C₄ alkyl; or R⁵ and R⁶ together are alkylene having 2 to 5 carbon atoms; R⁷ and R⁸ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; (12) SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; (13) --N(R^(c))C(O)R^(d) wherein R.sup. c and R^(d) are as defined; or (14) --CH₂ CH₂ OCH₃ or --CH₂ CH₂ OC₂ H₅ ; with the proviso that R⁷ is not at the 6-position; and R⁹ is C₂ -C₆ alkylene.
 10. The method of claim 9 wherein R is chlorine, bromine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, nitro, C₁ -C₂ alkylthio or C₁ -C₂ alkylsulfonyl; R¹ is hydrogen or methyl; R² is hydrogen or methyl; R³ is hydrogen or methyl; R⁴ is hydrogen or methyl; R⁵ is hydrogen or methyl; R⁶ is hydrogen or methyl; R⁷ and R⁸ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n is the integer 0 or 2; and R^(b) is (a) C₁ -C₂ alkyl; or (b) C₁ -C₂ alkyl substituted with halogen or (10) --CH₂ CH₂ OCH₃ or --CH₂ CH₂ OC₂ H₅ ; and R⁹ is C₂ -C₄ alkylene.
 11. The method of claim 9 wherein R is chlorine; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is 3-ethoxy; R⁸ is 4-methylsulfonyl; and R⁹ is ethylene.
 12. The method of claim 10 wherein R is nitro; R¹ is methyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is hydrogen; and R⁹ is ethylene.
 13. The method of claim 10 wherein R is chlorine; R¹ is hydrogen; R² is hydrogen; R³ is methyl; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is 3-ethyloxy; R⁸ is 4-CH₃ CH₂ SO₂ --; and R⁹ is ethylene.
 14. The method of claim 10 wherein R is nitro; R¹ is methyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is 4-CH₃ SO₂ --; and R⁹ is ethylene.
 15. The method of claim 10 wherein R is chloro; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is 3-chloro; R⁸ is 4-chloro; and R⁹ is ethylene.
 16. An herbicidal composition comprising an herbicidally active bis(2-benzoyl-3-oxo-cyclohexenyl)thioglycol.
 17. An herbicidal composition comprising an herbicidally active compound having the structural formula ##STR11## wherein R is halogen, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, nitro; cyano; C₁ -C₂ haloalkyl, or R^(a) SO_(n) -- wherein n is 0 or 2 and R^(a) is C₁ -C₂ alkyl;R¹ is hydrogen or C₁ -C₄ alkyl; R² is hydrogen or C₁ -C₄ alkyl; or R¹ and R² together are alkylene having 2 to 5 carbon atoms; R³ is hydrogen or C₁ -C₄ alkyl; R⁴ is hydrogen or C₁ -C₄ alkyl; or R³ and R⁴ together are oxo; R⁵ is hydrogen or C₁ -C₄ alkyl; R⁶ is hydrogen or C₁ -C₄ alkyl; or R⁵ and R⁶ together are alkylene having 2 to 5 carbon atoms; R⁷ and R⁸ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; (12) SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; (13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined; or (14) --CH₂ CH₂ OCH₃ or --CH₂ CH₂ OC₂ H₅ ; with the proviso that R⁷ is not at the 6-position; and R⁹ is C₂ -C₆ alkylene and an herbicidally acceptable carrier or adjuvant.
 18. The composition of claim 17 wherein R is chlorine, bromine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, nitro, C₁ -C₂ alkylthio or C₁ -C₂ alkylsulfonyl; R¹ is hydrogen or methyl; R² is hydrogen or methyl; R³ is hydrogen or methyl; R⁴ is hydrogen or methyl; R⁵ is hydrogen or methyl; R⁶ is hydrogen or methyl; R⁷ and R⁸ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n is the integer 0 or 2; and R^(b) is (a) C₁ -C₂ alkyl; or (b) C₁ -C₂ alkyl substituted with halogen or (10) --CH₂ CH₂ OCH₃ or --CH₂ CH₂ OC₂ H₅ ; and R⁹ is C₂ -C₄ alkylene.
 19. The composition of claim 18 wherein R⁷ is hydrogen, methylthio, methoxy, ethoxy, --CH₂ CH₂ OCH₃ or --CH₂ CH₂ OC₂ H₅ and is in the 3-position, and R⁸ hydrogen, chlorine, bromine, fluorine, trifluoromethyl or R^(b) SO_(n) wherein R^(b) is C₁ -C₃ alkyl and n is the integer 0 or
 2. 20. The composition of claim 18 wherein R is chlorine; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is 3-ethoxy; R⁸ is 4-methylsulfonyl; and R⁹ is ethylene.
 21. The composition of claim 18 wherein R is nitro; R¹ is methyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is hydrogen; and R⁹ is ethylene.
 22. The composition of claim 18 wherein R is chlorine; R¹ is hydrogen; R² is hydrogen; R³ is methyl; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is 3-ethoxy; R⁸ is 4-CH₃ SO₂ --; and R⁹ is ethylene.
 23. The composition of claim 18 wherein R is nitro; R¹ is methyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is 4-CH₃ SO₂ --; and R⁹ is ethylene.
 24. The composition of claim 18 wherein R is nitro; R¹ is methyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is 4-CH₃ SO₂ --; and R⁹ is butylene.
 25. The composition of claim 18 wherein R is nitro; R¹ is methyl; R² is methyl; R³ and R⁴ are oxo; R⁵ is methyl; R⁶ is methyl; R⁷ is hydrogen; R⁸ is 4-trifluoromethyl; and R⁹ is ethylene. 